Acylated naphthyl monoazophenyl dyestuffs



United States Patent V y ,20 ACYLATED NAPHTHYL MONOAZOPHENYL DYESTUFFS Werner Bossard and Hans E. Wegmuller, Riehen, near Basel, Switzerland, assignors to J. R. Geigy A.G., Basel,

Switzerland No Drawing. Filed Nov. 14, 1962, Ser. No. 237,759 Claims priority, application Switzerland, Nov. 17, 1961,

13,360/61 4 Claims. (Cl. 260-404) The invention concerns new, water dispersi-ble azo dyestuffs, processes for the production thereof, processes for the dyeing of hydrophobic synthetic textile material using the new dyestuffis and, as industrial product, the material dyed with the aid of these dyestuflFs.

It has been found that azo dyestufis which are difiicultly soluble in water are obtained if compounds of the Formula I OH CO-N' I in which A represents a phenyl radical which contains at least one electrophilic substituent which does not dissociate acid in water, in oor .p-position to the azo group, and Alkylene represents a lower alkylene radical with maximally 4 and preferably with 2 to 4 carbon atoms,

are reacted with acy-lating agents to form esters of the general Formula II wherein A and alkylene have the meanings given in Formula I and acyl represents the acid radical of the acylating agent.

The term electrophilic substituents which does not dissociate acid in water as used in this specification and the appended claims, of which substituents there are preferably not more than three present in A, means the nitro, cyano and trifiuoromethyl group, the carba'lkoxy groups, having not more than 8 carbon atoms, such as carboxylic acid methyl, ethyl or butyl ester groups, the unsubstituted, monoand disubstituted carbamoyl amide groups with maximally 8 carbon atoms, the unsubstituted, monoand disubstituted sulphonic acid amide groups, wherein amide is a radical with not more than 8 carbon atoms, 1 nitrogen atom and 0 to 1 oxygen atom, such as sulphonic acid dimethylamide, diethyl amide, dibutylamide, phenylmethylamide, piperidide and morpholide groups, phenoxy sulphonyl and chlorophenoxy sulphonyl radicals with maximally 8 canbon atoms; the keto groups with 2 to 8 carbon atoms such as acetyl, propionyl, butyroyl, benzoyl groups; the halogens fluorine, chlorine, bromine.

Further optional substituents compatible with the aforesaid electrophilic substituent or substituents in the benzene nucleus of A and designated in this specification Tsociate acid in water, with suitable hydroxyalkylamides ice as compatible substituents are alkyl with maximally 8 carbon atoms, such as methyl, ethyl, propyl, isopropyl, ter-t. amyl, isooctyl, cyclohexyl, benzyl, phenyl, methylphenyl, chlorophenyl; alkoxy with maximally 4 carbon atoms such as methoxy and ethoxy, which may be uptionally hydroxylated as, for instance, in 2-hydroxyethoxy; phenoxy; chlorophenoxy; methylphenoxy; acetylamino, chloroacetylarnino, B-chloropropionylamino, benzoylamino, chlorobenzoy-lamino, chloromethylsulphonylamino, chlorotriazinylamino and chloropyrimidylamino groups.

Since the dyestufs are d-iflicultly soluble, as has already been stated, water solubilising groups which dissociate acid in water such as -SO H or the --COOH group are excluded.

Preferably A is a phenyl radical which contains one to two of the aforesaid electrophilic substituents, which do not dissociate acid in water, in the oand p-position to the azo group.

The compounds according to the invention are produced by coupling diazonium compounds of the benzene series which contain, in 0- or p-position to the azo group, at least one electrophilic substituent which does not disof B-hydroxy-naphthoic acid.

The diazo components necessary for the production of preferred compounds of Formula I, usable according to the invention, in which A is an electrophilically substituted phenyl radical are, for example, 1-amino-2,4-dinitrobenzene and 1-ainino-Z-cyano-4-nitrobenzene.

The coupling components necessary for the production of compounds of Formula I, usable accordingto the invention are obtained, e.g., from esters of ,B-hydroxynaphthoic acid by reaction with lower primary hydroxyalkylamines.

The acylation of compounds of Formula I of the inven tion can be performed with carboxylic acid chlorides such as acetyl chloride, chloroacetyl chloride, propionyl chloride, butyryl chloride, benzoyl chloride, chlorobenzoyl chloride, 4-methylsulpl1onyl-lebenzoyl chloride, 4-nitrobenzoyl chloride, with sulphonic acid chlorides such as methyl sulphonic acid chloride, ethyl sulphonic acid chlorides, benzene sulphonic acid chloride, diethylamino sulphochloride or p-toluene sulphonic acid chloride, or with anhydrides such as acetanhydride, and also with ester chlorides of carbonic acid such as chlorocarbonic acid methyl ester, ethyl ester, propyl ester, butyl or ethoxyethyl ester.

The acylation is performed advantageously at a raised temperature, if necessary in the presence of an acid binding agent such as sodium acetate or pyridine. In certain cases it is of advantage to perform the reaction in suitable organic solvents such as chlorobenzene or dioxan.

It is surprising that the acylated dyestufifs according to the invention have considerably better affinity to polyester fibres than the starting materials. In addition they have increased drawing power, and the dyeings attained therewith have very good fastness to rubbing. Compared with i the known azo compounds of the phenyl-azo-Z-hydroxystituents in the diazo component, one of which is a nitro group in p-position to the azo bridge and the other 1s a nitro or cyano group in o-position to the azo bridge, also diifer from dyeings obtained with the known dyestuffs in their considerably increased fastness to light. Polyester fibres dyed with the last-mentioned dyestuffs according to the invention are distinguished by their excellent drawing power and very good fastness to rubbing, light and sublimation.

The dyestuifs according to the invention arebrought into easily distributable form by milling withdispersing agents. Suitable dispersing agents are, e.g. anionic such as alkylaryl sulphonates, condensation products of al dehydes, i.e. formaldehyde and naphthalene sulphomc acids, lignin sulphonates, or non-anionic such as fatty alcohol polyglycol ethers. Mixtures of these dispersing agents are used with advantage.

The dyestuffs according to the invention are suitable for the dyeing of hydrophobic synthetic textile fibres from aqueous dispersion, e.g. for the dyeing of cellulose (11- and tri-acetate, particularly however, for the dyeing of high molecular esters of aromatic polycarboxylic acids and polyfunctional alcohols, for example, glycol terephthalates such as Terylene of Imperial Chemical Industries, London, Dacron of E. I. du Pont de Nemours & Co., W1lmington, Delaware, U.S.A., Tergal f Rhodiaceta, Lyons, France, or Trevira of Farbwerke Hoechst, Frankfurt am Main, Germany. The dyestuffs can also be used, however, for the dyeing of synthetic polyamide fibres such as nylon of Du Pont de Nemours or of Perlon of Farbenfabriken Bayer, Leverkusen, Germany.

The dyeing of polyester fibres with aqueous disperslons of dyestuffs according to the invention is performed advantageously at temperatures of over 100 C. under pressure. However, the dyeing can also be performed at the boiling point of the water in the presence of carriers such as, e.g., phenylphenol, polychlorobenzene compounds or similar auxiliaries.

In individual cases, the drawing power of the dyestufifs can be even improved by mixing two or more of the dyestuffs according to the invention.

Depending on the composition of the dyestuffs, yellow, orange and red dyeings can be attained on polyester fibres which have very good fastness to rubbing, sublimation and light.

Preferred dyestuffs of the invention correspond to the formula 1 2 T H0 CONH alkylene O acyl a N e N 23 wherein n is an integer ranging from 1 to 2,

X is nitro,

X is nitro, cyano, chloro or bromo,

X is hydrogen, trifluoromethyl, alkoxycarbonyl having a total of maximally 8, and preferably not more than 5 carbon atoms, N-alkyl-substituted carbamoyl with maximally 8 carbon atoms, especially N,N-diethyl, carbamoyl, phenoxysulfonyl, methylphenoxysulfonyl, chlorophenoxysulfonyl, or N-alkyl-substituted, N-phenyl-substituted and N-phenyl-N-alkyl-substituted sulfamyl, all of said sulfamyl radicals having not more than 8 carbon atoms, especially N,N-diethylsulfamyl and N- phenyl-N-methylsulfamyl,

Z is hydrogen, chloro, bromo or fiuoro,

Alkylene is ethylene, propylene or butylene (i.e. an alkylene radical with 2 to 4 carbon atoms), especially 1,3-propylene, and

Acyl is the acyl radical of an acylating agent, having from 0 to 1 sulphur atom and from 1 to 10 carbon Particularly interesting among these preferred compounds are those of the formula wherein n, X X Z, alkylene and acyl have the meaning given under Formula III.

Dyestuffs of the invention which are particularly valuable because of their excellent drawing power and fast mess to light and sublimation are those of the formulas I NOFQN=N and C O NH-alkylene-O-acyl H O C 0 NH'alkylene-Oacyl I O N wherein alkylene and acyl have the meanings given under Formula III.

The following examples illustrate the invention. Where not otherwise stated, parts are given as parts by weight. The temperatures are in degrees centigrade. The relationship of parts by weight to parts by volume is as that of grammes to cubic centimetres.

EXAMPLE 1 12 parts of 1-(2'-nitrophenylazo)-2-hydroxynaphtha- Iene-B-carboxylic acid N B hydroxyethylamide and 60 parts of acetanhydride are boiled for 4 hours. After cooling, the whole is diluted with 200 parts of ethyl alcohol and 50 parts of water. The new dyestufr has the composition ?H GONCHzCHaOCOCHa and crystallises in the form of orange needles. The pre crpltate is filtered off, washed with ethyl alcohol and then with water and dried in vacuo at 60-70". Milled with a synthetic dispersing agent, the dyestulf so obtained dyes polyester fibres or cellulose triacetate fibres in pure scarlet shades from aqueous dispersion, possibly in the presence of carriers. The dyebath is substantially exhausted. The dyeings are fast to rubbing, sublimation and light.

Dyestuffs having equivalent properties are obtained if in the above example with otherwise the same procedure, 12 parts of the compounds given in column 1 of the following Table I are used as starting materials and acetylated.

Table I Colour of Starting material l iiiz i mi i fi si iii 0H (FONHCHzCHgOH 1 Orange:

OH OONHCHzCHzOH (|)H C|3ONHCH2CH2OH $1 ?H (IJONHCH2CH2OH 4 O Orange:

OH CONHCHzCHgOH 6 (02115) 2N r N=N D04 OH O ONHCH2OH2CH2OH 7 OzN -N=N OH O ONHCHzCHzCHzOH OH CONHCHZOH CHgOH EXAMPLE 2 of ethyl alcohol are added. The precipitate which forms of the composition 15 parts of l-(2-nitro-phenylazo)-2-hydroxynaphtha1- OH CONHOECHQOCOO ene-3-carboxylic acid-B-hydroxyethylamide in 250 parts 70 l of dioxan are heated for 8 hours at 100-110" with 50 QN=N parts of benzoyl chloride and 25 parts of anhydrous sodium acetate. The reaction mixture is then concentrated N in vacuo to about 100 parts after coohng 300 parts 75 is filtered oil. under suction, Washed with ethyl alcohol If in the above example, the 15 parts of starting material are replaced by equivalent amounts of the coupling products given in the first column of the following Table II and these are acylated under the conditions described in the above example with the corresponding number of parts by weight of the carboxylic acid chlorides given in column 2, then dyestuffs are obtained which produce polyester dyeings having similarly good properties.

Table 11 Shade of Carboxylic acid acylated N0. Starting material chloride dyestutf 011 polyester fibres on oonnomcmon 1 0HPQN= 0&150001 Scarlet.

on r zonnomomorr 2 OzNQ-N=N8 cimco c1 0- Orange.

- on r zonrromornorr a QZNQN=N 0H301-I20001 Do.

01 OH r loNncmomon 4 OgN-ON=N CHzCHzCOCl Do.

or or: ooNncniouzorr 5 O;N- N=N 0101120001 Do.

OH connorncmorr CoH5\. s /N-SO|- N= 010200001 Do.

011 oonnomornorr CeHs\, p 1 /N-SO -ON=N ouaouzcHicoclnu Do.

or: ooNHcHwmoH s mrrOn: onromcmcomun Scarlet.

on ooNnomomcnzorr 9 cm-Qn: 011301120001 Do.

or: ooNrromomon 1o OZNON=N CHaOHaCO 01 Orange.

I CN

OH $ONHCH2OH2CHZOOOCH3 is filtered off, washed first with ethyl alcohol and then with water and dried. A preparation obtained by milling the dyestuff obtained with a condensation product of naphthalene-Z-sulphonic acid and formaldehyde dyes polyglycol terephthalate fibres such as Dacron (Du Pont de Nemours, Delaware, U.S.A.) from an aqueous dispersion, possibly in the presence of a carrier such as the sodium salt of o-phenylphenol, in pure orange shades. The dye bath is substantially exhausted. The dyeings have very good fastness to washing, light and sublimation.

EXAMPLE 4 1 2 parts of 1-(2',4-dinitro-phenylazo)-2-hydroxynaphtha1ene-3-carboxylic acid-,B-hydroxyethylamide are heated for 8 hours at 100-110 with 200 parts of dioxar'i and 30 parts of benzoyl chloride and 20 parts of anhydrous sodium acetate. The reaction mixture is then concentrated in vacuo to about 75 parts and, after cooling, 200 parts of methyl alcohol are added. The precipitate formed is filtered off, washed with methyl alcohol and then with water and dried. The dyestufi is a scarlet powder which corresponds to the formula OH coNncr-nonzoo 0-6 A preparation obtained by milling with a condensation product of naphthalene-Z-sulphonic acid and formaldehyde dyes polygly col tereplrthalate fibres such as Terylene (I.C.I. London, England) from aqueous dispersion, possibly in the presence of carriers, in orange shades. The dyebath is substantially exhausted. The dyeings have very good fastness to Washing, rubbing, light and sublimation.

Dyestufis having similar properties are obtained if, in the above example, instead of 12 parts of starting material, equivalent amounts of the starting materials given column 1 of the following Table III are reacted under the usual conditions with the corresponding acylating agents given in column '2.

Table III Shade of acylated No. Starting material Aeylating agent dyestufi on polyester fibres 011 ooNnor-rzomon:

1 OzNN=N 011301120001 Orange I ON on oornzrcmomon 2 OzNO-N=N CHrS0zCL Do.

OH CONHGHzCHaOH a OzN--N=N 0H3--s0zo1---- Do. I V N 02 OH (IJONHCHrGH OH '4 OzNO-N=N ClOOOOzH Do.

OH oorruomomomon 5 O2NN=N ciooocznfi Do.

i ON

on: OONHOHzCHgCHzOH e OzNN=N OuH GOCl Do:

I ON

Table lIICntinued Shade of No. Starting material Acylating agent d; t 11f %n till 11 ooNncnzonzomon 7 OzN-N=N 00150001 Orange.

l lo:

0H ooNnonzonzcmon 8 OzN -N=N CHaC H4SOGl Do.

l lo:

on CONHCHzCHzOHzOH 9 O2NC N=N CHaCHzCHzCOOI Do.

l fl'oz OH ooNnornomomorr 1o 02N-C N=N 0H3s0201 Do.

ILTOZ EXAMPLE 5 4 parts of 1-(2'-nitro-4'-methyl-phenylazo)-2-hydroxynaphthalene-3-carboxylic acid-B-hydroxyethylamide in 200 parts of dioXan are heated for 8 hours at 110l20 with parts of p-toluene sulphonic acid chloride and 5 parts of anhydrous sodium acetate. After cooling, 100 parts of ethyl alcohol and 500 parts of water are added to the reaction mixture. The precipitate which forms is filtered off under suction, washed with methyl alcohol and then With Water and dried in vacuo at 6070. The dyestuff is a red powder and corresponds to the formula OH 00Nn01120HZos0i- -CHa Table IV Shade of acylated No. Starting material Acylating agent dyestufi on polyester fibres (31 C| H ICONHCHZOHZCHZCHZOH 1 2 8 TQ 2 1 o a e.

(EN (|)]EI IOONHOHzCHiCHzCHzOH 2 lTTOn 0H CONHCHzClzDCHzOH a 0iN-C N=N cm-O-som Do.

14 Table lVCntz"nued Shade of A V acylated No. Starting material Aeylating agent dyestufi on polyester fibres 1V0; )11 (IJONHCHZCHQQH 4 RHE)2N QN=N nt-Oman Orange.

17102 (|)H CONHCHzCHzOH 5 2 a D0.

OH (IIONHCHQCH2CH2OH s meQN-NQ wmcom Do.

l CH3 1 I0z 11 CONHCHzCH OH 7 Q PO aCO)2O-- Do.

IIIOZ (DH (IJONHOHzCHZOH a OzNON=N otnfioool Do.

EXAMPLE 6 EXAMPLE 8 3 parts of the dyestulf obtained according to Example 3 are dispersed in 4000 parts of water. 20 parts of the sodium salt of o-phenylphenol, 20 parts of diammonium phosphate are added to this dispersion and 100 parts of terephthalic acid ester yarn are dyed for 1 /2 hours at 95-98. The dyebath is substantially exhausted. The dyeing is rinsed and after-treated with dilute sodium hydroxide solution and a dispersing agent. In this way, a pure orange dyeing is obtained which is fast to rubbing, sublimation and light.

If in the above example, the 100 parts of polyester yarn are replaced by 100 parts of cellulose triacetate fabric, dyeing is performed under the conditions given and the dyeing is then rinsed with water, an orange dyeing having very good properties is obtained.

EXAMPLE 7 In a pressure dyeing apparatus, 2 parts of the dyestuff obtained according to Example 4 are finely suspended in 2000 parts of water which contains 4 parts of a synthetic dispersing agent. The pH of the dyebath is adjusted to 6-6.5 with acetic acid. 100 parts of terephthalic acid polyester fabric are introduced at 50, the bath is heated within minutes to 126-135 and dyeing is performed for minutes at this temperature. The dyebath is Well exhausted. The dyeing is then rinsed with water, soaped and dried. Under these conditions, an orange dyeing is obtained which is fast to washing, rubbing, light and sublimation.

The dyestuffs described in the other examples produce dyeings of equivalent quality by this process.

Polyglycol terephthalate fabric (such as Dacron of E. I. du Pont de Nemours, Wilmington, Delaware (U.S.A.) is impregnated in a foulard at 40 with a liquor of the following composition: a

20 parts of a dyestuff obtained according to Example 4, finely dispersed in 7.5 parts of sodium alginate,

20 parts of triethanolamine,

20 parts of octylphenol polyglycol ether, and 900 parts of water.

CONE-alkylene-O-acyl wherein n is an integer ranging from 1 to 2,

X is nitro,

X is a member selected from the group consisting of nitro, cyano, chloro and bromo,

X is a member selected from the group consisting of hydrogen, trifluoromethyl, lower alkoXy-carbonyl, N- lower alkyl-substituted carbamoyl, phenoxysulfonyl, methylphenoxysulfonyl, chlorophenoxysulfonyl, N- lower alkyl-substituted sulfamyl, N-phenyl-substituted sulfamyl and N-phenyl-N-lower alkyl-substituted sulfamyl,

| NOFQN=N Z is a member selected from the group consisting of 25 10 NOrON=N 3. A compound of the formula no ooNn-omom-o-ooc 4. A compound of the formula References Cited by the Examiner UNITED STATES PATENTS 2,219,280 10/40 Graenacher -2--- 260-156 2,323,314 7/43 Dickey et a1. 260-199 30 3,001,982 9/61 Krzikalla et a1. 260-204 X 3,057,673 10/ 62 Mills et a1. 854

FOREIGN PATENTS 648,768 8/37 Germany. 544,817 4/42 Great Britain.

CHARLES B. PARKER, Primary Examiner. 

1. A COMPOUND OF THE FORMULA 